Fuel oil composition containing combination of aliphatic and alkyl amines



United States Patent FUEL OIL COMPOSITION CONTAINING COMBI- NATION OF ALIPHATIC AND ALKYL AMINES Robert A. Moore, Sewell, N. J., assignor to Socony Mobil Oil Company, Inc., a corporation of New York No Drawing. Application November 18, 1954, Serial No. 469,841

3 Claims. (Cl. 44-72) This invention relates to improved fuel oil compositions. More particularly, it relates to the improvement of fuel oils which have been rendered non-clogging and which are particularly suitable for use as industrial and domestic fuels.

The fuel oils which are improved in accordance with' this invention are hydrocarbon fractions having initial boiling points of at least about 300 F. and end points not higher than about 750 F., and which boil substantially continuously throughout their distillation ranges. Such fuel oils are generally known as distillate fuel oils. It will be understood, however, that this term is not restricted to straight-run distillate fractions. As is Well known to those skilled in the art, the distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked distillate fuel oils, or mixtures of straight-run distillates, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well known commercial methods, such as, acid or caustic treatment, solvent refining, clay treatment, etc.

The distillate fuel oils are characterized by their relatively low viscosities, pour points and the like. The principal property which characterizes the contemplated hydrocarbon fractions, however, is the distillation range. As mentioned hereinbefore, this range will lie between about 300 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially continuously throughout its distillation range.

The fuel oils particularly contemplated herein are the Nos. 1, 2 and 3 fuel oils used in domestic heating and as diesel fuel oils, particularly those made up chiefly or entirely of cracked distillate stocks. The domestic heating oils generally conform to the specifications set forth in ASTM specifications D396-48T. The specifications for diesel fuels are defined in ASTM specifications character have a tendency to deteriorate in storage and to form sludge. This sludge, together with other impurities present in stored fuels, such as rust, dirt and moisture, causes the formation of insoluble products which settle out of the fuel and adhere to the surfaces with which they come in contact, eventually causing clogging of equipment parts, such as the screens and filters of burners and engines utilizing the fuel.

To combat the clogging problem, the prior art has proposed the addition to fuel oils of minor amounts of surface-active chemical agents which are capable of preventing the insoluble products formed in the fuel from being deposited on the equipment parts. These agents apparently inhibit the agglomeration of the insolubles, so that these materials more readily pass through screens, strainers, filters, nozzles, etc. Additives, such as primary, normal aliphatic amines of from 10 to 18 carbon atoms per molecule, have been found to be effective in 2,793,943 Patented May 28, 1957 this respect. Furthermore, it has been found, as dis- This particular mixture of amines, which is manufactured and sold by the Armour Company of Chicago, Illinois, under the trade name Armeen S has the following composition:

Percent Octadecadienyl amine 45 Octadecenyl amine 35 Octadecyl amine 10 Hexadecyl amine 1O Experience has shown, however, that certain of the primary, normal aliphatic amine additives, particularly those of 16 to 18 carbon atoms, have a serious drawback in that fuels to which they have been added, when stored for prolonged periods, develop an increased tendency to emulsify with water. Stored fuel oil, of course, normally becomes contaminated with water which condenses from the air on the container walls, and is normally susceptible to emulsification to a certain extent. These amine additives reduce this emulsification tendency upon initial addition to the fuel oil. However, after the fuel oil has been stored for a period of about six months or longer, it shows a greater tendency to emulsify than fuel to which no amine has been added. The exact reason for this is not known. Apparently, the amine additive, in the course of the storage period, forms a product in the fuel oil which has emulsifying properties. In any event, this increase in the emulsifying property of the fuel oil is highly undesirable because it greatly accelerates the corrosive action of the fuel oil on the various equipment parts, particularly purifying devices, such as screens, filters, etc. The Armeen S additive is particularly offensive in this respect. Thus, although Armeen S is an excellent anti-clogging agent, it is not satisfactory for use in fuels which are subjected to storage for prolonged periods due to its adverse effect on the emulsifying properties of the oil. Because of its high effectiveness from the standpoint of anti-clogging ability, however, it would be most desirable if means could be provided to overcome the deficiency of the Armeen S additive with respect to emulsification. Accordingly, it is a primary object of this invention to providea means for overcoming emulsification tendencies of fuel oils inhibited with Armeen S. A more specific object is the provision of fuel oil compositions containing anti-clogging amounts of Armeen S and which are stabilized against emulsification in storage. Other and further objects of the invention will become apparent from the following detailed description thereof.

The present applicant has found that a fuel oil which has been rendered non-clogging by the addition of Armeen S thereto may be stabilized against increase in its emulsification tendencies in storage by adding to it a second additive, viz., a tertiary alkyl, primary monoamine Typical amines are, for example, 1,1,3,3-tetramethylbu-tylamine (tertiary octyl amine), l,1,3,3,5 ,5-hexamethylhexylamine, 1,1,3,3,5,5,7,7, octamethyloctylamine, 1,1,

factured "and sold by the Rohm and Haas Company of Philadelphia, rs, under the trade names Primene 81 and "P-fimene JM. mary, alkylamine isomers having the tertiary alkyl structure above-defined and I containing. from: 12 to 15 carbon atoms per molecule. Primene IM is a mixture of tertiary-'alkyl'primary monoamineisomers, similar to Primene 8-1 but inwhich the" averagealkyl chain lengthis' frorn- 18' to 24 carbon atoms. Forfurth'erdescription of these amine mixtures, see Rohm h -Haas brochure SP-33 12/52, entitled, Tertiary-Alkyl Primary Amines The .fact thatthetertiary alkyl, primary monoamines have theability to-preservethe-fueloilfrom developing emulsifyingtendenciesin the presenceof Armeen' S is surprising in view of the fact that straight-chained, primary, aliphatic amines having from to 16 carbon atoms, which have been proposed in the prior art as superior de-emuls'ifying agents for fuel oils, do not have this ability. Since these latter amines are inferior to Armeen S as anti-screen clogging agents, it will be appreciated that a fuel oil containing a combination of Armeen S and-atertiary alkyl, primary monoamine of from -8 to 24 carbon atoms, as proposed by the present invention, is not only outstanding from the standpoint of non-clogging character, but also exhibits excellent nonemulsifying properties.

The following examples and tests will serve to illustrate the invention. In all of these examples and tests, the base fuel oil-used was a No. 2 fuel oil consisting of 60% distillate stock derived from continuous catalytic cracking, 25% 650 F. end point straight-run gas oil and 300- F. to 400 F. cut-back naphtha. This oil had a boiling range of from about 340 F. to about 650 F Example I A blend of the base fuel oil with Armeen S in a concentration of 50 pounds of the additive per 1000 barrels of the oil was prepared.

Example 2 A blend of the'base fuel oil with tertiary 'octyl, primary amine in a concentration of 50 pounds of the additiveper 1000 barrels of the oil was prepared.

Example 3 A blend of the base fuel oil with Primene 81 in a concentration of 50 pounds of the additive per 1000 barrels of the oil was prepared.

Example 4 A blend of the base fuel oil with Primeue JM in a concentration of 50 pounds of the additive per 1000 barrels of'the oil was prepared.

Example 5 Example 6 Ablndbfthe'basefuel oil with"50'p1ound s of.Armeen Primene -8'1"is a mixture.- of pri was prepared.

S and 25 pounds of tertiary octyl, primary amine per 1000 barrels of oil was prepared.

Example 7 A blend of the base fuel oil with 50 pounds of Armeen S and 25 pounds of PrimeneSl per 1000 barrels of 011 Example 8 A'blend of the base fuel oil with 50 pounds of Armeen S and 25 pounds 'of Primene JM per 1000 barrels of oil was prepared.

Example 9 For the purpose of comparison, a blend of the base fuel oil with 50 pounds. of Armeen S and 25 pounds of Armeen C per1000barrels of fuel oil was prepared.

The fuel oil blends described in the foregoing examples were subjected toemulsific'ation tests as follows: A series of tests were first conducted on portions of the freshly prepared blends. Other portions of each of the blends were aged by'all'owing themto stand for three weeks at F. The aged blends were then subjected'to emulsion tests. V

The testprocedureused in all "cases was as follows: A 200 milliliter portion of the fuel to be tested and 20 milliliters of' distilled water are placed in a clear glass pint bottle. The bottleis tightly capped and set in an Everback mechanical shaker in a horizontal position such that th'e maximum degree of agitation is afforded. The shakeris then'run' at its maximum setting for five minutes. The bottle is then removed and allowed to stand in an upright position in the dark for 24 hours. At the'end' of the 24-hour settling period, the appearance of the water layer is -noted.' The fuel layer is siphoned off, care being tak'en' not to disturb the oil-water interfaceand discarded. A fresh portion of the fuel oil being tested-is then. added. The described sequence of steps is then repeated, If no emulsion appears in the water layer'after this sequence has been performed ten times, the oil is considered to havepassed the test. On the other hand, if, afterany 24-hour settling period in the procedure, there is any degree of emulsificati-on in the water layer, the fuel is considered to have failed the test. This test procedure has been found to provide emulsions in inhibited oils similar to emulsions which occur in these same oils only after prolonged periods of normal handling and storage in the field on a commercial basis. The test results are summarized in Table I.

TABLE I v Emulsion Test Example Additive Added to Fuel 011 Number Initial Aged 1 Armeen' S Pass. Fail. Tertiary octyl, primary arnin Pass Pass. Primene 81 Pass. Pass. Primene .TM Pass. Pass. Armeen C Pass Pass. Armeen S+tertiary octyl, primary Pass Pass.

amine. Armean S+Primene 81 Pass... Pass. ArmeenS-kPrimene' JM Pass Pass. Armeen S-l-Armoen G Pass Fail.

1 Aged for three weeks at 80 F.

The tertiary alkyl primary amines, however, retain their die-emulsifying effectiveness in the presence of the Armeen S.

Generally, the "Armeen S" additive is utilized in the fuel oil as an anti-clogging agent in concentrations of from about 10 to about 100 pounds per 1000 barrels of oil, the preferred amount being from about 25 to about 50 pounds per 1000 barrels. It has been found that the amount of tertiary alkyl primary monoamine necessary to protect the fuel oil against development of emulsifying tendencies ranges from as little as about 3 pounds per 1000 barrels, when the concentration of the Armeen S in the oil is 25 pounds per 1000 barrels or less, up to about 10 pounds per 1000 barrels when the concentration of Armeen S is 100 pounds per 1000 barrels. This is illustrated in Table II which lists the results obtained in a series of emulsion tests using fuel blends containing various amounts of Armeen S and the Primene 81 in combination (Examples 10 to 28). In practice, it is contemplated to use somewhat more than the minimal elfective amounts of the tertiary alkyl, primary amine additive, say, 25 pounds per 1000 barrels of fuel oil, or higher, in order to insure its overall effectiveness with different fuel oils under varied conditions and periods of storage.

TABLE II Cone. of Cone. of Emulsion Test Example Number Armeen S, Primene 81,

lbs. 1,000 lbs/1.000

b ls. bbls. Initial Aged 1 25 Pass Borderline. 25 8 Pass Pass. 25 Pass Pass. 25 Pass Pass. 50 0 Pass- Fail. 60 1 Pass Fall. 50 2 Pass- Borderline. 50 3 Pass. Pass. 50 4 Pass Pass. 50 5 Pass. Pass. 50 10 Pass. Pass. 50 Pass- Pass. 75 0 Pass- Fail. 75 10 Pass Pass. 76 15 Pass- Pass. 75 Pass- Pass.

100 0 Pass- Fail.

100 10 Pass. Pass.

100 25 Pass- Pass.

1 Aged for three weeks at 80 F.

The additives of the invention may be prepared in the form of concentrated oil solutions containing specified quantities thereof. Such solutions are suitable for marketing and can be conveniently added to fuel oils in amounts to provide the desired improvements therein.

If desired, the fuel oil compositions contemplated herein and the additive concentrates, above-described, may also contain other addition agents designed to impart other improved characteristics to such fuel compositions. Thus, for, example, there can be present foam inhibitors, anti-rust agents, burning and ignition quality improvers, etc.

Although the invention has been described and illustrated herein by means of certain specific embodiments, it is not intended that the scope of the invention be limited in any way thereby, but only as indicated in the following claims.

What is claimed is:

1. A distillate fuel oil to which non-clogging properties have been imparted by incorporating therein from about 10 pounds to about pounds per 1000 barrels of a mixture of primary, normal aliphatic monoamines consisting of about 45% normal octadecadienyl amine, about 35% normal octadecenyl amine, about 10% normal octadecyl amine and about 10% normal hexadecyl amine and which also contains a minor amount, sufficient to stabilize said oil against the development of emulsifying properties in storage, of an alkyl amine selected from the group consisting of an alkyl amine having from 8 to 24 carbon atoms and containing the structural unit C NH1 and a mixture of such alkyl amines.

2. A distillate fuel oil to which non-clogging properties have been imparted by incorporating therein from about 10 pounds to about 100 pounds per 1000 barrels of a mixture of primary, normal aliphatic monoamines consisting of about 45% normal octadecadienyl amine, about 35% normal octadecenyl amine, about 10% normal octadecyl amine and about 10% normal hexadecyl amine and which also contains a minor amount, sulficient to stabilize said oil against the development of emulsifying properties in storage, of an alkyl amine of the formula 3. A distillate fuel oil to which non-clogging properties have been imparted by incorporating therein from about 10 pounds to about 100 pounds per 1000 barrels of a mixture of primary, norm-a1 aliphatic monoamines consisting of about 45% normal octadecadienyl amine, about 35% normal octadecenyl amine, about 10% normal octadecyl amine and about 10% normal hexadecyl amine and which also contains a minor amount, suflicient to stabilize said oil against the development of emulsifying properties in storage, of a mixture of alkyl amines having an average of from about 18 to about 24 carbon atoms per molecule and containing the structural unit CHI References Cited in the file of this patent UNITED STATES PATENTS 2,607,665 Duncan Aug. 19, 1952 2,672,408 Bonner Mar. 16, 1954 2,684,292 Caron July 20, 1954 OTHER REFERENCES Tertiary-Alkyl Primary Amines, Rohm and Haas, Philadelphia, Pa, September 1954, pages 16 and 17. 

1. A DISTILLATE FUEL OIL TO WHICH NON-CLOGGING PROPERTIES HAVE BEEN IMPARTED BY INCOROPATING THEREIN FROM ABOUT 10 POUNDS TO ABOUT 100 POUNDS PER 1000 BARRELS OF A MIXTURE OF PRIMARY, NORMAL ALIPHATIC MONOAMINES CONSISTING OF ABOUT 45% NORMAL OCTADECADIENYL MONOAMINES CON35% NORMAL OCADECENYL AMINE, ABOUT 10% NORMAL OCTADECYL AMINE AND ABOUT 10% NORMAL HEXADECYL AMINE AND WHICH ALSO CONTAINS A MINOR AMOUNT, SUFFICIENT TO STABLIIZED SAID OIL AGAINST THE DEVELOPMENT OF EMULSIFYING PROPERTIES IN STORAGE. OF AN ALKYL AMINE SELECTED FROM THE GROUP CONSISTING OF AN ALKYL AMINE HAVING FROM 8 TO 24 CARBON ATOMS AND CONTAINING THE STRUCTURAL UNIT 